Halomethyl ethers



Patented July 28, 1942 UNITED STATES PATENT OFFICE HALOMETHYL ETHERSHerman A. Bruson and Clinton W. MacMullen, Philadelphia, Pa., assignorsto Riihm & Haas Company, Philadelphia, Pa., a corporation of Delaware NoDrawing. Application October 15, 1941, Serial No. 415,036

9 Claims.

wherein hal is a member of the group consisting of chlorine and bromine,n is an integer less than three, R. is a carbocyclic aromatic radical, Xis a member of the group consisting of and S, A is an alkylene group,the chain of which may be interrupted by a member of the groupconsisting of O and S, and Y is a member, of the group consisting of--OH, -Oalkyl, O-aryl, --OCOalkyl, OCO--aryl, COalkyl, CO aryl, COOalkyl, COOH, and CI-Izha1.

These halomethyl compounds may be prepared by condensing an ether of thegeneral formula RFXAY with formaldehyde and hydrogen chloride orhydrogen bromide. The reaction takes place readily in concentratedhydrochloric or hydrobromic acid solution at temperatures of about 10-60C. without splitting the ether linkages. The compounds thus obtained maybe used in the preparation of wetting agents, resins, insecticides,mothproofing agents, tanning materials, and other industrial products.

Typical ethers which are suitable for the preparation of these newhalomethyl compounds are the following:

and compounds containing the radical ROA in which A is a polyalkyleneether group, such as in which R is an aromatic residue, which maycontain other nuclear substituents such as alkyl, aralkyl, cycloalkyl,aryl, nitro, halogen, acyl groups, etc. but must be free of radicals orgroups which are destroyed by the hydrogen halide or the formaldehyde.Such groups are, for ample, the amino, diazo, and aldehyde groups. tmust also be free of hydroxyl groups which wo cause condensation of theformaldehyde in a di erent manner. These aromatic radicals must h ve atleast one replaceable nuclear hydrogen atom and, in case more than oneis available, more than one (ha1CHz) group can be introduced into thearomatic radical. The aromatic radical may be mononuclear or polynuclearsuch as a benzene, naphthalene, phenanthrene, anthracene, or otherpolynuclear radical.

The reaction is carried out in general by suspending the aryl ether inthe aqueous hydrohalogen acid containing the formaldehyde and passing indry hydrogen halide at temperatures of about 10 to C. The aryl ether mayalso be dissolved in a suitable non-reactive organic solvent such aspetroleum ether, ethylene dichloride, etc. The formaldehyde may be usedin the form of an aqueous solution or as paraformaldehyde. The productsobtained are usually lowmelting solids or thick oils.

This invention may be illustrated by the following examples. It is notlimited, however, to the exact conditions of time, temperature, andreagents shown as it may be otherwise practiced within the scope of theappended claims.

Example 1 A stream of dry hydrogen chloride was passed into a mixture of100 grams of phenoxyethoxyethyl chloride, 102 grams of 37% formaldehyde,and 300 cc. of concentrated hydrochloric acid for 8 hours at atemperature of about 30 0., the reaction mass being stirred throughoutthis period. A light brown oil formed which was separated, dissolved inbenzene and washed with ice water. The benzene solution was dried withanhydrous sodium sulphate, filtered, and the solvent evaporated invacuo, leaving 116 grams of oil which on cooling changed to a whitesolid. This material was purified by distillation in vacuo. It boiled at210-215 C./ mm. and the distillate solidified to a crystalline masswhich on recrystallization from petroleum ether was obtained in the formof white crystals having a melting point of 52-54 C. The determinationof chlorine content showed it to be di(chloromethyl) phenoxyethoxyethylchloride having the probable formula:

Example 2 ClCHOO-CHrCHzCl Emample 3 A mixture of 122 grams ofphenoxyethoxyethoxyethyl chloride, 102 grams of 37% formaldehyde, and300 cc. of concentrated hydrochloric acid was stirred vigorously and astream of dry hydrogen chloride was passed into the mixture for 8 hoursat 30-33 C. A light brown oil separated which was dissolved in benzene,washed with ice water, the solution dried with anhydrous sodiumsulphate, filtered, and the henzene evaporated in vacuo. The residue wasa clear, light brown oil weighing 136 grams. A chlorine determinationshowed this to be di- (chloromethyl) phenoxyethoxyethoxyethyl chloridehaving the formula:

Example 4 A mixture of 44 grams of p-chloroethoxyethyl phenyl sulphide,ClC2H40C2H4S-C6H5, 65 grams of 37 formaldehyde, and 200 cc. ofconcentrated hydrochloric acid was heated at 50-60 C. and stirredvigorously while a stream of dry hydrogen chloride was passed throughthe mixture for 10 hours. A brown oil layer separated which wasdissolved in benzene, washed, dried, and the solvent removed in vacuo.50 grams of a clear, brown oil remained which was chloromethyl phenyl ,8chloroethoxyethyl sulphide having the formula:

A mixture of 118 grams of o-chlorophenoxyethoxyethyl chloride, grams of37% formaldehyde, and 300 cc. of concentrated hydrochloric acid washeated at 50-60 C. and stirred vigorously while a stream of dry hydrogenchloride was passed through the mixture for 18 hours. A brown oilseparated which was washed and dried as described above. On evaporationof the solvent a clear, light brown oil weighing 126 grams remained.This was chloromethyl 0- chlorophenoxyethoxyethyl chloride having theprobable formula:

0101100 crmo CzH4Cl Example 6 A mixture of 131 grams of o-sec-octylphenoxyethoxyethoxyethyl chloride, 60 grams of 37% formaldehyde, and 300cc. of concentrated hydrocloric acid was heated at 50-60 C. while astream of dry hydrogen chloride passed in for about 20 hours. Theproduct was isolated as described above. The light brown oil waso-secoctyl chloromethyl phenoxyethoxyethoxyethyl chloride having theformula:

In a similar manner dodecyl phenoxyethoxyethyl chloride was converted toits chloromethyl derivative which is a pale yellow oil.

Example 7 A mixture of grams of p-phenyl phenoxyethoxyethoxyethylchloride, 142 grams of 37% formaldehyde, and 300 cc. of concentratedhydrochloric acid was heated at 50-60 C. and stirred while a stream ofdry hydrogen chloride was passed in for 10 hours. 151 grams of a darkbrown oil was isolated in the usual manner. This product waschloromethyl p-phenyl phenoxyethoxyethoxyethyl chloride.

Example 8 81.6 grams of p-cyclohexyl phenoxyethoxyethoxyethyl chloride,41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloricacid were heated at 50-60 C. and a stream of dry hydrogen chloridepassed in for 11 hours. A clear, dark brown oil weighing 68 grams wasisolated as described above. The product obtained was p-cyclohexylchloromethyl phenoxyethoxyethoxyethyl chloride having the probableformula:

83.6 grams of p-benzyl phenoxyethoxyethoxyethyl chloride, 81 grams of37% formaldehyde, and 200 cc. of concentrated hydrochloric acid wereheated at 40-50 C. and a. stream of dry hydrogen chloride passed in for8 hours. The clear brown oil, separated as described above, waschloromethyl p-benzyl phenoxyethoxyethoxyethyl chloride.

COMPcU'ufl Example A mixture of 136.8 grams of dodecyl methylphenoxyethoxyethoxyethyl chloride, 60 grams of 37% formaldehyde, and 300cc. of concen trated hydrochloric acid was heated at 50-60 C. and astream of dry hydrogen chloride passed in for 27 hours. The red brownoil, isolated as described above, was chloromethyl dodecyl methylDhenoxyethoxyethoxyethyl chloride having the 10 probable formula:

CizHu-C1H2(CHs)OCzH4-OCzHl-OCaH4Cl HzCl Example 11 A mixture of 156grams of p-ter-octyl phenoxyethoxyethyl chloride, grams ofparaformaldehyde, and 150 grams of ethylene dichloride was stirred whilea stream of dry hydrogen chloride was passed in for 17 hours at about 30C. A red 29 oil layer separated which was washed with cold water, driedwith anhydrous sodium sulphate, filtered, and the ethylene dichloridedistilled off in vacuo. A clear, brown oil weighing 137 grams wasobtained. The .product was p-ter-octyl- 5 chloromethylphenoxyethoxyethyl chloride having the probable formula:

ter-CsH1 OCzHlOC 113401 Example 12 clear pale yellow oil remaining waschloromethylp-ter-octyl phenoxyethoxyethoxyethyl chloride.

Example 13 A mixture of 32 grams of o-phenyl phenoxyethanol, 75 grams of30% formaldehyde, and 90 cc. of concentrated hydrochloric acid washeated at 35-50 C. and a stream of dry hydrogen chloride passed in for 7hours. The product was isolated in the usual manner. It was an oil whichon analysis was found to be di(chloromethy1) -ophenyl phenoxyethanol.

Search Room passed in for 7 hours at 30-40 C. A resinous mass wasobtained which was washed and dried on a porous plate. Analysisindicated it to be the dichloromethyl derivative of phenoxy ethyl 5acetate.

Example 16 A mixture of 46 grams of o-nitro phenoxyethoxyethyl chloride,41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloricacid was stirred while a stream of dry hydrogen chloride passed in at30-60 C. for about 8 hours. A brown oil separated which was purified inthe usual manner. The product obtained was chloromethyl o-nitrophenoxyethoxyethyl chloride having the probable formula:

Example 17 A mixture of 80 grams of p-cyclohexyl phenoxyethoxyethyln-butyl ether, 51 grams of 37% formaldehyde, and 200 cc. of concentratedhydrochloric acid was stirred while a stream of dry hydrogen chloridewas passed in at 30-50 C. for 7 hours. A clear yellow oil was obtainedwhich was chloromethyl p-cyclohexyl phenoxyethoxyethyl n-butyl etherhaving the probable formula:

C6H11CeH3(CH2C1) OCzH4OC2H4OC4Ha Example 18 A mixture of 156 grams ofp-ter-octyl phenoxy- 35 ethoxyethyl chloride, 30 grams ofparaformaldehyde, and 150 grams of petroleum ether (B. P. 30-60 C.) wasstirred while a stream of dry hydrogen chloride was passed in for 16hours at 30-60 C. The turbid brown solution was washed with cold water,dried with anhydrous sodium sulphate, filtered, and the solventdistilled off in vacuo. A brown oil remained which was chloromethylp-ter-octyl phenoxyethoxyethyl chloride.

Example 19 A mixture of 26 grams of phenoxyethoxyethoxyethyl sulphide,41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloricacid was vigorously stirred while a stream of dry hydrogen chloride waspassed in for about 8 hours without heating or cooling. A very viscouslayer separated which was washed and dried on a porous plate. The brownelastic mass was tetra (chloromethyl) phenoxyethoxyethoxyethyl sulphidehaving the probable formula:

Example 14 A mixture of 76 grams of phenoxy acetic acid, 90 grams of 37%formaldehyde, and 300 cc. of concentrs .ed hydrochloric acid was heatedat 50-60 C. and a stream of dry hydrogen chloride passed in for 6 /2hours. A viscous mass separated which was washed and dried on a porousplate. Analysis showed the product to be di- (chloromethyl)phenoxyacetic acid.

Example 15 A mixture of 90 grams of phenoxy ethyl acetate, 90 grams of37% formaldehyde, and 300 cc. of concentrated hydrochloric acid wasstirred while a stream of dry hydrogen chloride was Example 20 A mixtureof 104 grams of butyl phenoxy acetate, grams of 37% formaldehyde, and300 cc. of concentrated hydrochloric acid was stirred while a stream ofdry hydrogen chloride was passed in for 7 hours without heating orcooling. A yellow layer formed which was dissolved in benzene, washed,dried, and the benzene removed in vacuo. A clear yellow oil remainedwhich was butyl dichloromethyl phenoxy acetate having the probableformula:

mom-Qocmcoocm.

Example 21 A mixture of 87.5 grams of phenoxyethoxyethyl dodecyl ether,61 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloricacid was stirred while a stream of dry hydrogen chloride was passed inwithout heating or cooling for 11 hours. The oil layer which separatedwas purified as described above. The product was a clear amber oil whichwas di(chloromethyl)- phenoxyethoxyethyl dodecyl ether having theprobable formula:

0101100 cgrno czrnocurm The bromo-methyl and di(bromomethyl) derivativesof compounds of the above type may be obtained by replacing the hydrogenchloride with hydrogen bromide. In some cases the aryl polyalkyleneether halides give resinous products which are diflicult to isolate.o-Methoxy phenoxyethoxyethyl chloride gives a viscous concentrateanalyzing for the dichloromethyl derivative. fi-Naphthoxy-ethoxyethylchloride when treated with formaldehyde and hydrochloric acid yields aresinous chloromethyl derivative.

Example 22 A mixture of 125 grams of diisobutyl phenoxy ethanol, 182grams of 37% aqueous formaldehyde, and 200 grams of concentratedhydrochloric acid was stirred and saturated with gaseous hydrogenchloride at 40-50 C. for 8 hours. The oil layer was taken up in benzene,washed with ice water, dried, and the solvent evaporated off underreduced pressure. The clear, yellow oil obtained was chloromethyldiisobutyl phenoxy ethanol.

Example 23 A mixture of 97 grams of diethylene glycol di- (diisobutylo-cresyl) ether 100 grams of 37% aqueous formaldehyde, and 200 grams ofconcentrated hydrochloric acid was stirred and saturated with gaseoushydrogen chloride at 60-70 C. for 16 hours. The oil layer was taken upin benzene, washed, dried, and the solvent removed in vacuo. About 30%conversion to chloromethyl diethylene glycol di-(diisobutyl o-cresyl)ether was indicated by chlorine analysis of the clear brown oilobtained.

Example A mixture of 245 grams of diethylene glycol diphenyl etherC6H5OC2H4OC2H4OC6H5, 300 grams of dioxane, and 490 grams of 37% aqueousformaldehyde was stirred and saturated with gaseous hydrogen chloridefor 16 hours at 40-60 C. The reaction mixture was poured into ice waterand an oil layer separated. The oil was taken up in benzene, washed,dried, and the solvent removed in vacuo. The clear, amber oil was amixture containing trichloromethyl diethylene glycol diphenyl ether anddichloromethyl diethylene glycol diphenyl ether.

Example 26 A mixture of 199 grams of 2,6-dichloro-4- ter.amylphenoxyethoxyethoxy benzene 243 grams of 37 aqueous formaldehyde, and200 grams of concentrated hydrochloric acid was stirred and saturatedwith gaseous hydrogen chloride at 40-60 C. for 8 hours. The oil layerwas separated, taken up in benzene, washed, dried, and the solventdistilled off under reduced pressure. The residual oil was2,6-dichloro-4- ter.amyl phenoxyethoxyethoxy chloromethyl benzene.

Example 27 A mixture of grams of diisobutyl-phenoxyethoxyethoxyethyldodecyl ether,

46 grams of 30% aqueous formaldehyde, and 200 grams of concentratedhydrochloric acid was stirred and saturated with gaseous hydrogenchloride at 4555 C. for 25 hours. The oil layer was taken up in benzene,washed with ice water, dried with anhydrous sodium sulphate, and thesolvent evaporated off under reduced pressure. The amber oil obtainedwas chloromethyl-diisobutyl-phenoxyethoxyethoxyethyl dodecyl ether. Thisapplication is a continuation-in-part of United States applicationSerial No. 228,145, filed September 2, 1938, now U. S. Patent No.2,266,737, issued December 23, 1941, in which there are claimed thosecompounds of the formula wherein Y is chlorine or bromine. There areclaimed herein those compounds in which Y is hydroxyl, oxyalkyl, oroxyaryl. The alkyl group may be a short or long chain, a branched orstraight chain, such as methyl, ethyl, butyl, isobutyl, heptyl, octyl,isooctyl, dodecyl, cetyl, octadecyl, etc. As an aryl group there may beused any of the aromatic nuclei which have been described above assuitable for R, including aryl groups having halomethyl substituents.

We claim:

1. Compounds of the formula wherein he] is a member of the groupconsisting of chlorine and bromine, n is an integer less than three, Ris a carbocyclic aromatic radical, X is a member of the class consistingof oxygen and sulfur, A is an alkylene group, the chain of which may beinterrupted by a member of the class consisting of oxygen and sulphur,and Y is a member of the group consisting of OH, Oalkyl, ar '1 Oaryl.

2. Compounds of the general formula wherein n is an integer less thanthree, R is a carbocyclic aromatic radical, A is a polyalkylene etherchain, and Y is a member of the class consisting of OH, Oalkyl, andOaryl.

3. Compounds of the general formula wherein n is an integer less thanthree, R is a phenyl group, A is a polyalkylene ether chain andUUMPUUNDS,

Y is a. member of the class consisting of OH, ()-alkyl, and -Oaryl.

4. A compound of the formula (ClCHz) n-R (OCHzCHz) yOalkyl wherein n isan integer less than three, R is a.

phenyl group, and y is an integer from one to ten inclusive.

5. A compound of the formula (ClCI-Iz)n-R-O-CHzCH2-O-CHzCH2Oalkylwherein n is an integer less than three and R is a phenyl group.

6. A compound of the formula (01cm) nR(OCH2CH2) v-CH wherein n is aninteger less than three, R is a.

Search Room phenyl group, and y is an integer rrom one to ten inclusive.

7. A compound of the formula (CICHz) nROCH2CH20CH2CH2-OC12H25 wherein nis an integer less than three and R is H a HERMAN A. BRUSON.

CLINTON W. MACMULLEN.

